Pesticidal uses of thiosubstituted phenols



United States Patent US. Cl. 424-225 9 Claims ABSTRACT OF THE DISCLOSUREA method for the control of undesirable pests, such as fungi, mites,beetles and flies, comprises applying a toxic amount of a particulartype of thiosubstituted phenol to the locus of the pest. The thiophenolemployed is of the formula:

In this formula, X is alkylene of 2 to 8 carbon atoms; R is lower alkyl;R is halogen; R is either hydrogen, hydrocarbyl or acyl; and n is 1 or2; m is from 0 to 4, inclusive; q is from 0 to -(m+n), inclusive; p isfrom 0 to 2, inclusive; p is 0 when R is other than hydrocarbyl; and thesulfur atom is separated from the phenol nucleus by at least two carbonatoms.

This is a division of our application S.N. 262,375, filed Mar. 4, 1963,now US. Patent 3,336,393, granted Aug. 15, 1967.

This invention relates to novel compositions of matter and to processesfor producing them. More specifically the present invention is concernedwith novel phenolic sulfides and to processes for the preparationthereof.

3,443,012 Patented May 6, 1969 The novel compositions of the instantinvention are best represented by the following formula:

wherein the substituent X is an alkylene radical of at least two carbonatoms, but preferably three to eight carbon atoms, the R substituent islower alkyl, the R substituent is halogen, R is a substituent selectedfrom the group consisting of hydrogen, hydrocarbyl, acyl, and mixturesthereof, n is an integer from one to two inclusive, m is an integer from0 to 4 inclusive, q is an integer from 0 to 5 (m+n) the integer p is 0when the substituent R is other than hydrocarbyl, the sulfur atom beingseparated from the phenol nucleus by at least two carbon atoms, butpreferably by 3 to 8 carbon atoms.

The alkylene radical X may be either unsubstituted or substituted bylower alkyl, hydrocarbyloxymethyl, hydrocarbylthiomethyl,2-(hydrocarbyloxy)ethyl, Z-(hydrocarbylthio)ethyl radicals, orhydrocarbyloxy radicals.

The term hydrocarbyl as used herein represents the radical obtained byremoval of a hydrogen atom from a hydrocarbon, and thus encompassesalkyl, alkenyl, cycloalkyl, phenyl, naphthyl, alkylphenyl, other aryl,benzyl, and other arylalkyl. While no necessary limitations are imposedby the chemistry of the invention upon the size of the hydrocarbylradical, for economic and other reasons the preferred hydrocarbylradicals are those having from 1 to about 20 carbon atoms.

Consequently, the term alkyl as used herein has no chemically-imposedupper limit but for economic and other reasons alkyl radicals of from 1to about 20 carbon atoms are preferred. The term lower alkyl as usedherein refers to alkyl radicals having from 1 to 6 carbon atoms.

The term acyl as used herein has its ordinary meaning, that is, theradical derived by removal of OH from an acid. Here also there is nochemically imposed upper limit but for economic reasons acyl radicals offrom 1 to 20 carbon atoms are preferred.

Illustrative examples of X substituents include CH(CH )CH CH(OCH and thelike.

Illustrative examples of the R substituents include methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl,l-methylbutyl, isoamyl tertamyl, l-ethylpropyl, and hexyl, as well asother lower alkyl, where m 1, the R groups may be alike or different.

Examples of the group R are fluorine, chlorine, bromine, and iodine,where q l, the R groups may be alike or different.

Examples of the R substituent include hydrogen, methyl, ethyl, propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl,cyclohexyl, octyl, nonyl, decyl, dodecyl, octadecyl, allyl,methoxyethyl, hydroxyethyl, chloropropyl, phenyl, tolyl,tert-butylphenyl, p-chlorophenyl, 2,4,5 trichlorophenyl, benzyl, 2phenylethyl, p-chlorobenzyl, acetyl, propionyl, butyryl, benzoyl,thiobenzoyl, cyano, N-methylcarbamoyl, N-methylthiocarbamoyl,N,N-dimethylcarbamoyl, N,N-dimethylthiocarbamoyl, other N- andN,N-di(hydrocarbyl)substituted carbamoyl and thiocarbamoyl,dimethoxyphosphinyl, diethoxyphosphinyl, dimethoxythiophosphinyl,diethoxythiophosphinyl, other di(lower alkoxy) phosphinyl andthiophosphinyl, and O-alkylthiocarbonyl, for example.

A preferred group of new phenols of the present invention possesses ahigh level of biological activity, a relatively lower cost andrelatively greater ease of manufacture. This preferred group has theformula:

CHCH CHZSO R t,

wherein the substituents R R R, m, and p are as above defined, q=4m, andR is selected from the group consisting of hydrogen, lower alkyl,lower-alkoxymethyl; and 2-(lower-alkoxy)ethyl.

Examples of compounds within this preferred group include the following:

2- 3-mercaptopropyl phenol 2- 3-methylthiopropyl 3,4,5,6-tetramethylphenol 2- (3 methylthiopropyl)3,4,5,6tetrachlorophenol 2- (3 methylthiopropyl 4-b romo phenol 2- (3octadecylthiopropyl 4-fiuoro phenol 2- 3-tolylthiopropyl) 4-iodophenol2-( 3-ethylthiopropyl )-4-hexylphenol 2- 3-ethylthio-1- [methoxymethyl]propyl phenol 2- 3-methy1thio-1- [2-methoxyethyl] propyl phenol 2-3-acctylthio- 1 [2-butoxyethyl] propyl phenol 2-(3-pheuylthio-1-[hexyloxymethyl]propyl) 4-chlorom-cresol 4 2- 3-[dimethoxythiophosphinylthio]-1-[methoxy methyl] pro pyl phenol 2- 3benzylthio-1-[benzyloxymethyl]propyl)6-tertbutylphenol 2-3-methylthiopropyl) 6-tert-butyl-p-cresol 2- (3 cyclohexylthiopropyl5-is0propylphenol as well as examples given in more detail hereinafter.

Illustrative examples of the broader group of compounds of the presentinvention include: 2-(1-methyl-7- methylthioheptyl)phenol, 4 (3cyclohexylthiomethyl) phenol, 2-(2-ethylthioethyl)phenol, 2,6 di(3methylsulfinylmethyl phenol.

While methods have been available in the past for preparing phenolspossessing sulfide substituents attached directly to the ring orseparated from the ring by one carbon atom, there have been no methodsfor the synthesis of phenols possessing sulfide substituents separatedfrom the ring by two or more carbon atoms, and such phenols have nothitherto been known nor their valuable properties anticipated.

Furthermore, although there are many examples of the addition of RSH tosimple olefins, no examples have been known of the addition of RSH tounsaturated phenols. In fact phenolic compositions are well knowninhibitors of free radical additions and have been known to inhibit theaddition of RSH to simple olefins.

Surprisingly, the novel compositions of the present invention whereinthe integer p is 0 are readily prepared by the addition, in the presenceof a free radical catalyst, of thiol compositions having the formulaRSH, wherein R is a substituent as defined herein, to alkenylphenols ofthe following formula where the X substituent represents an alkenylradical corresponding to X and differing from X only in that X possessesa carbon to carbon double bond; and R R m, q, and n are as definedherein.

The preferred group of compositions of the present invention are derivedfrom o-allylphenols of the following formula:

wherein the substituents R R R and the integers m: and q are as definedherein. When the substituent R is lower alkoxymethyl or2-(lower-alkoxy)ethyl, the unsaturated phenols are prepared as describedin our copending application Ser. No. 260,076, filed Feb. 20, 1963.

The novel process of the present invention to prepare the phenolswherein the integer p is 0 is conducted by admixing the desired thiolRSH with the side-chain unsaturated phenol described above andsubjecting said mixture to free radical reaction-initiating conditionsamongst which are: heating; exposure to actinic light; addition of afreeradical catalyst, or combinations of these initiating conditions.Reaction conditions utilizing actinic light and/or free-radicalcatalysts are preferred where R- is other than0,0-dialkoxythiophosphinyl but where R is 0,0-dialkoxythiophosphinyl,purely thermal initiation is preferred. Where the unsaturated chaingroup X in the phenolic starting material has the double bond locateda,B-(i.e. adjacent) to the phenol ring, the group RS becomes attached tothe 5 carbon atom and the H-atom of the thiol RSH becomes attached tothe a-carbon atom, regardless of method of initiation and regardless ofthe nature of R. Where the group X in the phenolic starting material hasthe double bond in the [3, position and said double bond is terminal,then the RS group becomes attached to the terminal ('y) carbon atom andthe H becomes attached to the penultimate (13) carbon atom when thereaction is initiated by light or free radical catalysts. However, whenthe reaction is initiated by thermal means, as in the case of the0,0-dialkylphosphorodithiolates, the addition may go in both directionsto some degree, giving a mixture of isomers, but giving predominantlythe isomer having the RS group on the terminal carbon atom.

Where the double bond in X is [3,7 or further removed from the phenolring but not terminal, the addition generally goes both ways, to yield amixture. Suitable free radical catalysts include organic peroxides suchas benzoyl peroxide, acetyl peroxide, cumene hydroperoxide, and ingeneral any organic compound of the structure QOOH or QOOQ where Q is amonovalent organic radical, also azo compounds of the type QN=NQ such asazobisisobutyronitrile, or any other organic compound which at suitablereaction temperatures, in the range of 40 to +2.50 centigrade, breaksdown to give free radicals. Inorganic free radical generators such ashydrogen peroxide or oxygen may also be used.

As indicated, the reaction may be conveniently run in the range of 40 to+250 centigrade although some- What higher or lower temperatures are notprecluded. A preferred temperature range is 20 to 200 centigrade.Atmospheric pressure is convenient although subor superatmosphericpressures are workable. When a gaseous RSH compound such as methylmercaptan is employed, moderately superatomspheric pressures may beadvantageous to hold the mercaptan in the liquid phase. When RSH is H S,superatmospheric pressures are advantageous.

No solvent is generally required although the use of an inert solvent ispossible. Suitable inert solvents are hydrocarbons such as benzene,heptane, petroleum ether, toluene, or the like, chlorinated hydrocarbonssuch as methylene chloride, ethylene chloride, chlorobenzene, or thelike, alcohols such as methanol or phenol, ketones such as acetone,esters such as ethyl acetate, or an access of one or the other reactantor product serving as solvent.

The novel compounds wherein p is l or 2 are conveniently prepared fromthe corresponding phenols where p is 0 by oxidation utilizing one or twomolar equivalents, respectively, of any suitable sulfide oxide agentsuch as hydrogen peroxide, peracetic acid, performic acid, perbenzoicacid, chromic acid, molecular oxygen in the presence of a catalyst (suchas N 0 or other oxidants capable of oxidizing sulfides.

The products of the invention may be isolated by distillation,fractional crystallization (where they are solids) or by differentialextraction. In the latter case, what is meant is that an alkalineextraction medium such as aqueous sodium carbonate or caustic may beemployed to leach out the relatively more acidic unreacted or excess RSHfrom the relatively less acidic phenolic product.

The phenols of the invention are highly active germicides, antioxidants,fungicides, miticides, insecticides, and insect repellents. They arealso useful chemical intermediates, for example for preparation ofpesticidal esters and ethers, in particular the carbamates described inour copending application filed on even date herewith. Also ofconsiderable insecticidal value are the 0,0-di(loweralkyl) phosphatesand thiophosphates of the phenols of the invention. Also of value asinsect repellents are the O-acyl and O-alkyl derivatives of the phenolsof the invention, possessing in many cases a higher degree of repellentactivity than the pareut phenol.

Also of pesticidal value as herbicides are the monoand dinitrationproducts of those phenols of the invention having unsubstituted orthoand/or para positions prior to nitration.

Also included in the present invention are the corresponding salts ofthe phenol compounds such as the sodium, potassium, zinc, lead andbarium salts. The salts can be prepared by reacting the appropriatephenol with the appropriate base such as NaOH. The salts are useful aschemical intermediates, oil additives and fungicides.

It is, of course, appreciated that the non-metallic salts are alsoincluded within the scope of the invention such as the triethylammoniumsalt and the like.

To further illustrate without intending to limit the invention, thefollowing examples are given.

Example 1 In a vessel fitted with a cooling jacket, stirrer and a lightwell for irradiating the contents with mercury vapor light were placed50 parts by weight of o-allylphenol and 0.5 part ofazobisisobutyronitrile catalyst. The vessel was purged with nitrogen,then pressured with methyl mercaptan. Over two and one-half hours, 18parts of methyl mercaptan was fed into the vessel while stirring,irradiating the contents, and holding the temperature at 30 to 40degrees centigrade. After addition was complete, the irradiation wascontinued at 40 degrees centigrade for 7 hours. The product mixture wasthen fractionally distilled to obtain 44 parts of o-(3-methylthiopropyl)phenol, boiling point 104 to 108 degrees centigrade (0.1 mm.) as well asa foreshot of recovered o-allylphenol which was recycled to the nextbatch.

Analysis.Calculated for C H OS: Neutralization equivalent 182. Found:Neutralization equivalent 183.

Similar results, except for slightly lower conversion, were obtainedomitting either the light or the azobisisobutyronitrile. Theneutralization equivalent in this example as in all examples hereinafterwas determined by potentiometric titration of the phenol in pyridinesolution using 0.1 N tetrabutylammonium hydroxide in pyridine as thetitrant, the end point being taken as the point of inflection on anautomatically recorded graph of electrode millivoltage versus volume ofadded titrant.

Example 2 A mixture of 5 parts (by weight) of 2-allyl-5-methylphenol, 10parts methyl mercaptan, and 0.1 part of azobisisobutylronitrile wasexposed to the light of a mercury vapor lamp in a vessel fitted with a.reflux condenser cooled to below the boiling point of methyl Inercaptan.The reaction mixture was held at 30-40 degrees by external cooling.After seven hours, vacuum 'was applied to remove the unreacted methylmercaptan. The remaining liquid was fractionally distilled, to obtain 5parts of 2.-(3-methylthio propyl)-5-methylphenol, boiling point 108-110degrees centigrade (0.1 millimeter).

Analysis-Calculated for C H SO: Neutralization equivalent 198. Found:Neutralization equivalent 200.

Examples 3-25 The examples summarized in the following table wereperformed by the method of Example 2 (i.e. utilizing approximately 1percent azobisisobutyronitrile as catalyst as well as mercury vaporlight) except where otherwise indicated by footnotes.

Example 26.-Preparation of o-(3-methylsulfinylpropyl)phenol To asolution of 20 parts of o-(3-methylthiopropyl) phenol in 50 parts ofacetic acid was added slowly 13.9 parts of 30 percent aqueous hydrogenperoxide at 10-15 degrees centigrade over 30 minutes. The mixture wasthen stirred 2 hours at 20-30 degrees, then heated 20 minutes withsteam. It was then stripped free of solvent at 100 degrees (0.1millimeter pressure) leaving the product as 21, parts of clear viscoussyrup, soluble in water. The infrared spectrum showed the characteristicsulfoxide band at 9.76 microns.

Analysis.Calculated for C H SO Neutralization equivalent, 19 8. FoundNeutralization equivalent (nonaqueous potentiometric titration) 198.

Example 27.-Preparation of o-(3-methylsulfonylpropyl) phenol To asolution of 20 parts of o-(3-methylthiopropyl) phenol in glacial aceticacid was added slowly 28 parts of 30 percent aqueous hydrogen peroxideover 30 rninutes at 5-1-0 degrees, then the mixture was warmed slowly to100 degrees and held at 100 degrees for 60 minutes. It was stripped freeof solvent at 100 degrees (0.1 mm.), the residue then taken up inbenzene, the solution Washed with sodium bicarbonate solution and thenwith Water, and the benzene then stripped off under vacuum leavingbehind the desired sulfone as a slightly colored viscous syrup.

Analysis.-Calculated for C H SO Neutralization equivalent, 214. Found:Neutralization equivalent, 212.

Example 28.Preparation of o-(3-ethylsulfinylpropyl)phenol In the mannerof the above example, 10 parts of o- (ethylthiopropyl)phenol in 10 partsof acetic acid was reacted with 6.5 parts of 30 percent hydrogenperoxide to obtain the crude sulfoxide as a solid which wasrecrystallized from benzene-heptene to obtain 8.5 parts of colorlesscrystalline water-soluble solid, M.P. 99.5101 Centigrade. The infreredspectrum confirmed that the product was the desired sulfoxide on thebasis of characteristic sulfoxide bands at 9.7-10 microns.

Analysis.Calculated for C I-1 8: Neutralization equivalent 216. Found:Neutralization equivalent 214.

Example 29.-Preparation of o-(3-n-butylsulfinylpropyl)phenol In themanner of the preceding example, 10 parts ofo-(3-n-butylthiopropyl)phenol was reacted with 5.8 parts of 29 percenthydrogen peroxide to obtain 8 parts of the desired sulfoxide as acolorless viscous syrup, showing the expected infrared sulfoxide bandsat 9.7-10.0 microns.

Example 30.Preparation of o-(3-n-octylsulfinylpropyl phenol In themanner of the preceding example, parts of o-(3-n-octylthiopropyl)phenolwas reacted with 2.23 parts of 29 percent hydrogen peroxide to obtain3.5 parts of the desired sulfoxide as a viscous syrup, showing theexpected infrared sulfoxide bands at 9.7- microns.

Example 31.Preparation of o-(3-phenylsulfinylpropyl)phenol In the mannerof the preceding example, 5 parts of o-(3-phenylthiopropyl) phenol wasreacted with 2.67 parts of 29 percent hydrogen peroxide to obtain 4parts of the desired sulfoxide as a viscous colorless syrup, showing theexpected infrared sulfoxide bands at 9.7-10 microns.

Example 32.-Preparation of o-(3-methylsulfinyl) -p-cresol In the mannerof the preceding example, 30 parts of o-(3-methylthiopropyl)-p-cresolwas reacted with 18 parts of 29 percent hydrogen peroxide to obtain 35parts of the desired sulfoxide as a light yellowish viscous syrup,showing the expected infrared sulfoxide bands at 9.7-10 microns.

Example 33.2-(3-methylsulfinylpropyl)-3,4,6-trichlorophenol and methylether thereof To 10 parts of2-(3-methylthiopropyl)-3,4,6-trichlorophenol (prepared as describedabove) in 30 parts of glacial acetic acid was added 4.0 parts of 30percent hydrogen peroxide at 5-10 percent. After ten hours, the mixturehad deposited copious solids. The mixture was partially evaporated andthe solids were removed by filtration, and dried in air to obtain 9parts of colorless crystals, melting point 147-148.5 degrees.

' Analysis.Calculated for C H O SCl NE. 301.5. Found: NE. 299.

By conversion of this phenol to its sodium salt using equimolar sodiumethoxide in ethanol, isolation of the dry sodium salt by evaporation ofthe ethanol, and treatment with equimolar methyl sulfate in refluxingmethyl ethyl ketone, there was isolated the methyl ether of theabove-described phenol as a light tan crystalline solid, melting point78-785 degrees.

Analysis.-Calculated for C H O SCl S 10.13. Found: S 10.28.

Example 34.Preparation of o-(3-mercaptopropyl)phenol A mixture of 20parts of o-(3-acetylthiopropyl)phenol, 12 parts of sodium hydroxide and100 parts of water was refluxed for three hours under a nitrogenatmosphere, then filtered with activated charcoal, and the filtrateacidified by addition of hydrochloric acid. The oil thus liberated wasextracted with methylene chloride, the methylene chloride solution waswashed and then dried over magnesium sulfate. The solvent was thenstripped off and the crude product fractionally distilled to obtain acolorless liquid, boiling point 120-135 degrees (0.05-0.08 millimeter)which exhibited the characteristic mercaptan odor and infrared -SH bandat 3.9 microns, as well as the phenolic hydroxyl band at 3 microns.

The same thiol is produced by exposure of a mixture of 10 parts ofhydrogen sulfide and 10 parts of o-allylphenol plus 0.2 part ofazobisisobutyronitrile in a sealed Pyrex pressure vessel (underautogenous pressure of the hydrogen sulfide) to the light from a mercuryvapor are for 20 hours, at 20-30 degrees followed by fractionaldistillation of the reaction mixture.

Example 35.-Fungicidal activity Chemical: controlO-(3-acetylthiopropyl)phenol 50 0-(3-ethylthiopropyl)phenol 100O-(dimethoxy thiophosphinylthiopropyl)phenoL 50 O-(diethoxythiophosphinylthiopropyl) phenol 0-(3-isopropylthiopropyl)phenol 750-(3-methy1thiopropyl)-pcresol 2-(3-methylthiopropyl)-3,5-dimethylphenol100 0- 3-n-butylthiopropyl phenol 75 0-( 3-tert-butylthiopropyl) phenol100 2-(3-methylthiopropyl)-4-chlorophenol 100 0-( 3-octylsulfinylpropyl)phenol 50 0- 3-phenylsulfinylpropyl phenol 50 Approximate percentagereduction of leaf area affected by 1111 ew.

Example 36.-Fungicidal activity Tomato plants infested with spores ofAlternarz'a solani,

1 1 the causative fungus of Early Blight Disease, were sprayed withaqueous dispersions of various of the compounds of the invention at 0.04percent concentration. Infested plants were also left unsprayed forcomparison. The percent control of the disease (reduction of leaflesions) was estimated one week later.

Percent disease Chemical: control -(3-ethylthiopropyl)phenol 710-(3-acetylthiopropyl)phenol 790-(dimethoxythiophosphinylthiopropyl)phenol 920-(diethoxythiophosphinylthiopropyl)phenol M- 720-(3-n-butylthiopropyl)phenol 63 0-(3-phenylthiopropyl)phenol 700-(3-benzylthiopropyl)phenol 66 O-(3-methylthiopropyl)-p-cresol 77Example 37.Acaricidal activity Red spider mites on nasturtium leaveswere sprayed with an 0.1 percent aqueous dispersion ofo-(diethoxythoxythiophosphinylthiopropyl)phenol. After 24 hours, 99percent mortality of all mites originally present was observed. At thesame concentration malathion produced a 95 percent mortality.

Example 38.-Insecticidal activity Bean plants infested with third instarlarvae of the Mexican bean beetle were sprayed with 0.1% aqueousdispersions of o (dimethoxythiophosphinylthiopropyl) phenol, andforty-eight hours later were inspected for insect damage. It was foundthat none of the bean leaves were damaged by larval feeding, and that 60percent of the larvae were dead and the remainder were in a moribundcondition.

Similarly infested but unsprayed bean plants inspected at the same timewere found to be substantially defoliated by larvae feeding.

Example 39.Insecticidal activity Caged adult housefiies (Muscadomestica) were sprayed with 1 percent and 0.1 percent aqueousdispersions of various of the compounds of the invention. The percentageknockdown was observed two hours after spraying and the percentage kill24 hours after spraying, with the fol lowing results:

o- 3- hen lsulfinyl ropyl henol: 2

( p y p )p 24 hr. kill Example 40.Insect repellent activity Leaves ofbean plants infested with larvae of the Mexican bean beetle were sprayedwith 0.1 percent aqueous dispersions of 0-(3-octylthiopropyl) phenol ando-(3octylsulfinylpropyl)phenol, leaving parts of each plant unsprayed.When observed after 48 hours, the larvae were found to have migratedfrom the sprayed leaves. Although few dead larvae were found, thesprayed leaves were nevertheless completely protected from being eatenby the larvae by the repellant action of the chemicals.

What is claimed is:

1. A method for the control of undesirable pests selected from the groupconsisting of insects, mites, and fungi which comprises applying to thelocus of said pests an effective amount of a composition of the formulawherein the substitutent X is an alkylene radical of from 2 to 8 carbonatoms, the R substituent is lower alkyl, the R substituent is halogen, Ris a substituent selected from the group consisting of hydrogen,hydrocarbyl and acyl, n is an integer from 1 to 2 inclusive, m is aninteger from 0 to 4 inclusive, q is an integer from 0 to 5-(m+n)inclusive and p is an integer from 0 to 2, inclusive, the integer p is 0when the substituent R is other than hydrocarbyl, and the sulfur atom isseparated from the phenol nucleus by at least two carbon atoms.

2. A method according to claim 1 wherein the substituent X representsalkylene of from 2 to 8 carbon atoms, the R substituent is lower alkyl,the R substituent is halogen, R is a hydrocarbyl substituent selectedfrom the group consisting of alkyl, alkenyl, cycloalkyl, phenyl,naphthyl, alkyl phenyl and benzyl, said substituents being of l to about20 carbon atoms, wherein n is an integer from 1 to 2 inclusive, m is aninteger from 0 to 4 inclusive, q is an integer from 0 to S-(m-i-n)inclusive, the sum of m-l-n-l-q is 1 to 5, and p is an integer from 1 to2 inclusive, and the sulfur atom is separated from the phenol nucleus byat least two carbon atoms.

3. A method according to claim 2 wherein the composition is of theformula wherein R is lower alkyl; R is halogen, R is selected from thegroup consisting of hydrogen, hydrocarbyl, acyl and mixtures thereof; inis from 0 to 4 inclusive; p is from 0 to 2 and is 0 when R is other thanhydrocarbyl; q is 4m and R is selected from the group consisting ofhydrogen, lower alkyl, lower-alkoxymethyl; and 2-(l0wer-alkoxy) ethyl.

4. A method according to claim 1 wherein the treated are fungi and thecomposition employed is ethylthiopropyl) phenol.

5. A method according to claim 1 wherein the treated are fungi and thecomposition employed is methylthiopropyl)-p-cresol.

6. A method according to claim 1 wherein the treated are fungi and thecomposition employed is tert-butylthiopropyl) phenol.

7. A method according to claim 1 wherein the treated are mites and thecomposition employed (diethoxythiophosphinylthiopropyl) phenol.

8. A method according to claim 1 wherein the treated are insects and thecomposition employed (diethoxythiophosphinylthiopropyl) phenol.

9. A method according to claim 1 wherein the pests treated are insectsand the composition employed is o-(3- ethylthiopropyl) phenol.

pests o-(3- pests is opests is 0- (References on following page) 13References Cited UNITED STATES PATENTS 7/1965 Ladd 260-609 ALBERT T.MEYERS, Primary Examiner.

11/1950 Mikeska et a1 260 461 D. M. STEPHENS, Assistant Examiner.

2/1954 Chenicek 260-609 6 3/ 1958 Birum 1 7 30 US. Cl. X.R. 5/1963Richter 260-461 260953; 424300, 301, 335, 337

